CN115572063B - Photothermographic variable glass with low melting temperature and preparation method thereof - Google Patents
Photothermographic variable glass with low melting temperature and preparation method thereof Download PDFInfo
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- CN115572063B CN115572063B CN202211053514.4A CN202211053514A CN115572063B CN 115572063 B CN115572063 B CN 115572063B CN 202211053514 A CN202211053514 A CN 202211053514A CN 115572063 B CN115572063 B CN 115572063B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/04—Compositions for glass with special properties for photosensitive glass
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
Abstract
The invention provides photo-thermal refraction glass with low melting temperature and a preparation method thereof, which mainly relate to the technical field of diffraction optics, wherein cations of the photo-thermal refraction glass comprise the following components in percentage by mole: si (Si) 4+ ：54.0～63.0％、Na + ：24～36％、K + ：0～2％、Zn 2+ ：0～6％、Al 3+ ：4～11％、B 3+ ：0～10％、Ag + ：0.005～0.10％、Ce 4+ ：0.005～0.10％、Sn 2+ ：0～0.1％、Sb 3+ :0 to 0.1 percent; the anions of the photothermographic element contain Br ‑ 、O 2‑ And F ‑ Wherein, the mole percent of anions is as follows: br (Br) ‑ /O 2‑ ×100：0.30～1.0、F ‑ /O 2‑ ×100：3.0～5.8。
Description
Technical Field
The invention mainly relates to the technical field of diffraction optics, in particular to photo-thermal sensitive refractive glass with low melting temperature and a preparation method thereof.
Background
The volume Bragg grating based on photo-thermal refraction glass has the advantages of diffraction efficiency reaching more than 99%, independence of polarization, stable thermomechanical property, high laser damage threshold value and the like, has good wavelength and angle selectivity in the visible light to near infrared region, is widely applied to aspects of near-field light beam quality control, pulse broadening and compression, spectrum control, spectrum synthesis and the like, and becomes an ideal device of a high-power laser system. For example, the reflective type Bragg grating device can be used for the output spectrum locking and narrowing of a semiconductor laser pumping source of a strong laser device; the transmission type Bragg grating device can be used for optimizing the quality of a laser near-field light beam; chirped volume bragg grating devices can be used for pulse compression and stretching.
F, br is a very volatile component in photothermographic, refractive glass compositions. Wherein the volatilization amount of F reaches 5-20%, and the incident amount of Br reaches 25-45%. The fluctuation of the components directly affects the refractive index modulation characteristics of the photothermographic element, which is disadvantageous for mass production of Yu Tibu Bragg gratings. Therefore, how to control the volatilization of components and improve the batch stability of glass is one of the difficulties in the preparation of photo-thermal refraction glass.
Disclosure of Invention
The invention aims to provide photo-thermal sensitive fold-change glass with low melting temperature and a preparation method thereof, which solve the technical problems of how to control component volatilization and improve batch stability of glass in the prior art.
The invention discloses photo-thermal refraction glass with low melting temperature, which comprises cations in mole percent: si (Si) 4+ ：54.0～63.0％、Na + ：24～36％、K + ：0～2％、Zn 2+ ：0～6％、Al 3+ ：4～11％、B 3+ ：0～10％、Ag + ：0.005～0.10％、Ce 4+ ：0.005～0.10％、Sn 2+ ：0～0.1％、Sb 3+ ：0～0.1％；
The anions of the photothermal sensitive refractive glass contain Br-, O 2- And F-, and anion-cation nuclear balance, wherein, in mole percent of anions:
Br-/O 2- ×100：0.30～1.0、F - /O 2- ×100：3.0～5.8。
further, the cations of the photothermographic element glass, in terms of mole percent of cations, are represented by: si (Si) 4+ ：54.0～63.0％、Na + ：24～36％、K + ：0～2％、Zn 2+ ：0～6％、Al 3+ ：4～11％、B 3+ ：0～10％、Ag + ：0.005～0.10％、Ce 4+ ：0.005～0.10％、Sn 2+ ：0～0.1％、Sb 3+ :0 to 0.1 percent;
the anions of the photothermal sensitive refraction glass are formed by Br - 、O 2- And F - Composition, and anion-cation nuclear balance, wherein, in mole percent of anions:
Br - /O 2- ×100：0.30～1.0、F - /O 2- ×100：3.0～5.8
further, the mole percentage of the total of anions and cations is as follows: (Na) + +K + -F - -Br - )/2(Zn 2+ +0.5Al 3+ +0.5B 3+ )：1.695～1.815。
Further, the mole percentage of the total of anions and cations is as follows: (Na) + +K + -F - -Br - )/2(Zn 2+ +0.5Al 3+ +0.5B 3+ )：1.700～1.815。
Further, si in mole percent of cations 4+ :54.0 to 60%, and/or Na + ：29～36％。
Further, it contains, in mole percent of anions: br-/O 2- X 100:0.60 to 0.85, and/or F-/O 2- ×100：4.0～5.8。
Further, the glass melting temperature ranges from 1255 to 1310 ℃, preferably from 1255 to 1290 ℃.
Further, the glass transition temperature Tg is 440 to 455 ℃, preferably 440 to 450 ℃.
Further, the refractive index modulation degree of the glass is 180 to 1250ppm, preferably 500 to 1250ppm.
Further, the 780nm light absorption coefficient of the glass is in the range of 0.030-0.050cm -1 Preferably 0.037-0.050cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The light absorption coefficient of 1064nm is in the range of 0.005-0.015cm -1 Preferably 0.009-0.015cm -1 。
The second purpose of the invention is to protect a preparation method of photo-thermal sensitive fold glass with low melting temperature, after fully and uniformly mixing the raw materials, melting the raw materials into glass liquid at 1255-1310 ℃, clarifying and defoaming the glass liquid at 1450-1500 ℃, and then cooling the glass liquid to 1300-1350 ℃ for stirring and homogenizing; injecting the mixture into a mould preheated to 300-400 ℃ for molding, and introducing nitrogen to promote cooling of the surface of the glass, so as to ensure that the glass is not devitrified; and (3) cooling and shaping the glass, and putting the glass and the mold into an annealing furnace for cooling and annealing to obtain a colorless and transparent photo-thermal refraction glass block.
A third object of the present invention is to protect the use of a photothermographic, low melting temperature, refractive index glass for the preparation of diffractive optical devices, preferably for the preparation of volume bragg grating devices in the near infrared band.
A fourth object of the invention is to protect a glass preform, made of the above glass.
A fifth object of the invention is to protect an optical element, made with the glass described above or with the glass preform described above.
A sixth object of the invention is to protect an optical instrument, made with the glass or with the optical element described above.
Compared with the prior art, the invention has the following beneficial effects:
1. the photo-thermal sensitive fold-change glass of the invention uses Na 2 O-Al 2 O 3 -SiO 2 Based on system glass, F and Br crystal components are introduced, ceO is used 2 Is a photosensitizer, and uses Ag 2 O is a glass material prepared by a nucleating agent. The principle is that the glass is Ce under the condition of ultraviolet exposure of 310-30 nm 3+ Ion loses electron e to Ce 4+ Ion, ag + Capturing electrons to Ag 0 . And heating the glass sheet to 450-550 ℃ for heat treatment. Heat treatment process, ag 0 Collecting the particles in the exposure region, and then adding Ag 0 The particles grow NaF microcrystals as crystal nuclei. Since the refractive index of NaF is far lower than that of glass, a microcrystalline region with the refractive index lower than that of matrix glass can be formed at an exposure position, so that refractive index modulation is realized, and the method can be used for preparing volume Bragg gratings;
2. the volatilization of the components mainly occurs in the raw material melting stage and the high-temperature clarification and bubble removal stage. The reduction of the glass melting temperature, the reduction of the high-temperature viscosity of the glass and the reduction of the clearing bubble temperature are effective measures for inhibiting volatilization of photothermographic refraction glass components and improving the batch stability of the glass. The melting temperature of the photo-thermal refraction glass is as low as 1255-1310 ℃, which is favorable for controlling the volatilization of key components and improving the batch stability of the glass. The transition temperature Tg reaches 460-480 ℃, the refractive index modulation degree can reach 1250ppm, the light absorption coefficient of 780nm is 0.030-0.050cm < -1 >, and the light absorption coefficient of 1064nm is 0.005-0.015cm -1 Can be used for preparing the volume Bragg grating device with high diffraction efficiency, in particular to the volume Bragg grating device with near infrared band.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments.
The effect of each chemical component (constituent) in the glass of the present invention will be described in detail below, in this specification, the content of each cationic component, the total content being a mole percentage of the molar amount of the cationic component to the total molar amount of all the cationic components, unless otherwise specified; the content of the anionic component, the total content, is the mole percent of the molar amount of the anionic component to the total molar amount of all anionic components; the content ratio between the cationic components is the ratio of mole percentages between the cationic components; the content ratio between the anionic components is the ratio of mole percentages between the anionic components; the ratio between the anionic and cationic components is calculated according to the total mole amount of all the anionic and cationic components being hundred percent.
Si 4+ Is a glass network former, made of [ SiO ] 4 ]The tetrahedral building blocks form an irregular continuous network, forming the framework of the glass. Si (Si) 4+ The content is increased, and Tg of glass can be increased to enhance thermal stabilityThe method is favorable for inhibiting phase separation in the glass heat treatment process and reducing the light absorption coefficient of the glass subjected to exposure heat treatment, but excessive glass viscosity, high melting temperature and large volatilization of glass components influence the stability of the content of volatile components such as F, br. Si (Si) 4+ The reduction in the content is favorable for lowering the melting temperature of the glass and inhibiting volatilization of components in the glass melting process, but too little content can lead to easy phase separation in the glass heat treatment process, so that the light absorption coefficient of the glass subjected to exposure heat treatment is increased, and the Tg temperature is lowered accordingly, so that the thermal stability is poor. Thus, si in mole percent of cations 4+ The content of (C) is in the range of 54.0 to 63.0%, preferably 54.0 to 60%.
Zn 2+ 、Al 3+ Is a glass network intermediate, respectively prepared from [ ZnO ] 4 ]、[AlO 4 ]Tetrahedra enter the glass network structure and all play a role in providing network channels for the formation of NaF microcrystals. But at the same time increase Na + 、F - 、Br - Solubility in glass is unfavorable for the formation of NaF crystallites, affecting the refractive index modulating ability of the glass. Thus, when Zn 2+ 、Al 3+ In the case of increasing, the refractive index modulation ability of the glass is not affected, na + F- +Br-should be increased accordingly. On the premise of this, zn 2+ The refractive index modulation degree of the glass can be increased by increasing the amount of Zn 2+ Substitution of Al 3+ The melting temperature of the glass can be reduced, but too much glass can lead to lower Tg temperature, poor thermal stability and increased light absorption coefficient of the glass after exposure heat treatment; conversely, when Zn 2+ The reduction of Tg of the glass can increase the thermal stability, and the light absorption coefficient of the glass subjected to exposure heat treatment is reduced, but the refractive index modulation degree is reduced. Thus, zn in mole percent of cations 2+ The content range of (2) is 0-6%.
Al 3+ Increasing the Tg temperature of the glass can improve the thermal stability, is beneficial to inhibiting the phase separation in the glass heat treatment process and reducing the light absorption coefficient of the glass subjected to the exposure heat treatment, but too much can reduce the refractive index modulation degree of the glass and increase the melting temperature. Al (Al) 3+ Reducing the refractive index modulation degree of the glass and loweringLow melting temperatures, but too low, lower the glass Tg temperature, lower the thermal stability, and result in an increase in the light absorption coefficient of the exposed heat treated glass. Thus, al in mole percent of cations 3+ The content range of (2) is 4-11%.
B 3+ Is a glass network intermediate, in order to [ BO ] 4 ]Tetrahedra enter the glass network structure, increase the network strength of the glass, raise the Tg temperature of the glass, and can reduce the melting temperature of the glass. However, the excessive introduction easily causes phase separation and opacification in the glass heat treatment process, so that the light absorption coefficient of the glass after exposure heat treatment is increased. Thus, B is calculated as mole percent of cations 3+ The content range of (2) is 0-10%.
Na + 、K + The glass network external body is used as a cosolvent, can reduce the melting temperature of the glass, is beneficial to reducing volatilization of glass components and improves the stability of F, br and other volatile components in the glass. Wherein Na is + As a microcrystalline forming component, na + The increase of the refractive index modulation degree of the glass can be increased, but the excessive glass can cause easy phase separation and opacification in the heat treatment process of the glass, the light absorption coefficient is increased, the Tg temperature is also reduced, and the heat stability is poor. Conversely, na + The reduction is beneficial to reducing the light absorption coefficient of the glass subjected to exposure heat treatment, and improving the Tg temperature of the glass, but too little can reduce the refractive index modulation degree of the glass. Thus, in mole percent of cations, na + The content of (2) is in the range of 24 to 36%, preferably 29 to 36%.
K + Too much KBr crystal phase is easily formed, resulting in a decrease in refractive index modulation of the glass. Thus, K is calculated as mole percent of cations + The content range of (2) is 0-2%.
Ag - The more the crystal nucleus agent is introduced, the easier Ag is formed during exposure 0 Is beneficial to improving the refractive index modulation degree of the glass. However, excessive introduction amount can lead to crystallization in the unexposed area of the glass, reduce the refractive index modulation degree of the glass and easily corrode the platinum crucible in the glass melting process. Thus, ag is expressed as mole percent of cations + The content of (C) is in the range of 0.005-0.100%.
Ce 4+ Is a photosensitive ion in the glass and is partially converted into Ce during the glass melting process 3+ Ion, ce in glass in the ultraviolet light exposure process of 310-330 nm 3+ Is excited by photons to generate photoelectrons, which are formed by Ag + Ion capturing electrons to form silver atoms Ag 0 . Silver atom Ag during heat treatment 0 Nucleation of Ag 0 And (3) cluster crystal nuclei. The more Ce is introduced, the more Ce is formed 3+ The more, the more favorable the improvement of the photosensitivity of the glass, the more Ag is formed under the same exposure dose 0 Is beneficial to improving the refractive index modulation degree of the glass. But too much is introduced due to Ce 3+ The intrinsic broadband absorption at 300-325 nm can make the absorption of the corresponding wave band too strong, and influence the exposure uniformity of the glass in depth in the grating writing process. Thus, ce in mole percent of cation 4+ The content of (C) is in the range of 0.005-0.10%.
Sn 4+ Can inhibit the Ag of the unexposed area of the glass 0 The formation of the glass is reduced, crystallization in the unexposed region is reduced, and the refractive index modulation degree of the glass can be improved. However, excessive amounts can cause the glass to be easily phase-separated and opacified during heat treatment, resulting in an increase in the light absorption coefficient. Thus, sn in mole percent of cations 4+ The content of (C) is 0-0.10%.
Sb 3+ Ce can be used as sensitizer 4+ Reduction to Ce 3+ ，Sn 4+ Reduction to Sn 2+ Partially converted to Sb 5+ The photosensitivity of the glass is improved. At the same time Sb 3+ 、Sn 2+ Can inhibit Ag0 from changing into Ag-during the heat treatment process, and improve nucleation density. Introducing a proper amount of Sb 3+ The refractive index modulation degree of the glass is improved, the phase separation in the glass heat treatment process can be restrained, and the light absorption coefficient is reduced. But too much is introduced and too much Sb is formed in the glass 5+ During exposure with Ag - E competing for, but rather, reducing the refractive index modulation of the glass. Thus, in mole percent of cations, sb 3+ The content of (C) is 0-0.10%.
The anions of the photothermographic element of the invention contain Br - 、O 2- And F - And the charge of anions and cations reach balance, wherein:
Br - can reduce F - Solubility in glass, promoting the formation of NaF crystallites in the absence of Br - In the case of (2), it is difficult to form NaF crystallites, so Br - Is an essential component of photothermographic glass. In addition Br - Can also promote Ag 0 Cluster nucleation is an increase in the number of NaF crystallites in the glass. But Br - Too many KBr crystallites are formed, so that the refractive index modulation degree of the glass is reduced. Thus, in the glass composition, br is controlled - /O 2- The range of x 100 is 0.30 to 1.0, preferably 0.60 to 0.85, and a larger refractive index modulation degree can be obtained.
The more the content of F element is as the main component of NaF microcrystal formation, the more the refractive index modulation capability of the glass is improved. In addition, the introduction of F has the effect of reducing the high temperature and low viscosity of the glass and lowering the melting temperature. However, excessive F element introduction easily causes difficult control of heat treatment crystallization, excessive grain size growth, and easy phase separation in the glass heat treatment process, so that the light absorption coefficient is increased. Thus, in the glass composition, F is controlled - /O 2- The range of x 100 is 3.0 to 5.8, preferably 4.0 to 5.8, and a larger refractive index modulation degree and a lower melting temperature can be obtained.
In the present invention, na + +K + 、F - +Br - 、Zn 2+ +0.5Al 3+ +0.5B 3+ The three are related to each other and control (Na + +K + -F - -Br - )/2(Zn 2+ +0.5Al 3+ +0.5B 3+ ) The ratio is 1.695-1.815, preferably 1.719-1.815. The ratio determines the proportion of non-bridging oxygen introduced by alkali metal ions, and can obtain a larger refractive index modulation degree and a lower melting temperature. The excessively large ratio can lead to lower transition temperature Tg and poor thermal stability, and the glass is easy to split phase in the heat treatment process, so that the light absorption coefficient is larger; when the ratio is too small, na can be used for NaF crystallite growth - Insufficient refractive index modulation degree is small, and the melting temperature is too high.
The glass preparation method comprises the following steps:
selecting a glass formula, preparing raw materials according to the proportion of glass components (components), introducing the raw materials according to the formation of oxides, fluorides or salts, weighing the raw materials according to the weight ratio, adding the raw materials into a platinum crucible or a ceramic crucible after fully and uniformly mixing the raw materials, melting the raw materials into glass liquid at 1255-1310 ℃, clarifying and removing bubbles at 1450-1500 ℃, and stirring and homogenizing at 1300-1350 ℃; pouring the melted glass liquid into a metal mold preheated to about 300-400 ℃ for molding, and introducing nitrogen to promote the cooling of the surface of the glass, so as to ensure that the glass is not devitrified; and (3) cooling and shaping the glass, and putting the glass and the metal mold into an annealing furnace for cooling and annealing to obtain a colorless and transparent photo-thermal folded glass block. Those skilled in the art can appropriately select the raw materials, the process methods, and the process parameters according to actual needs.
[ glass preform and optical element ]
The optical glass thus produced may be used to produce a glass preform by using, for example, polishing, reheat press molding, precision press molding, or other press molding means. That is, the glass preform may be produced by mechanically working the optical glass by grinding or polishing, or by producing a preform for press molding from the optical glass, and then performing the polishing after the hot press molding, or by performing the precision press molding on the preform produced by the polishing.
The means for producing the glass preform is not limited to the above-described means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for performing hot press molding, precision press molding, and the like to produce optical elements such as lenses and prisms.
The glass preform and the optical element of the present invention are each formed of the optical glass of the present invention described above. The glass preform of the present invention has excellent characteristics possessed by an optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide various optical elements such as lenses and prisms having high optical value.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
[ optical instruments or devices ]
The optical element formed by the optical glass can be used for manufacturing optical instruments or devices such as diffraction optical instruments or devices, structural optical instruments or devices, high-resolution high-speed holographic recording instruments or devices and the like.
The performance index method of the invention is as follows:
[ melting temperature ]
The raw materials listed in the present invention having a melting temperature of 1.5Kg were charged into a 3L crucible and sufficiently melted to the lowest furnace temperature of the glass solution within 30 minutes. The melting temperature of the photothermographic glass of the present invention ranges from 1255 to 1310 ℃, preferably from 1255 to 1290 ℃.
[ transition temperature Tg ]
Tg (transition temperature) tests were carried out according to standard GB/T7962.16-2010. The photo-thermal refractive glass transition temperature Tg of the invention reaches 440-455 ℃, preferably 440-450 ℃.
[ refractive index modulation degree ]
Processing glass into 2-5 mm thick sheet with wavelength of 325nm and dosage of 2.5J/cm 2 After exposure to ultraviolet light, a heat treatment is performed simultaneously with the unexposed glass sheet. The crystallization temperature was 520℃and the crystallization time was 60 minutes. After completion of the heat treatment, refractive index test was performed according to standard GB/T7962.1-2010, refractive index difference Δnd=nd Unexposed glass -nd Exposure glass The refractive index modulation degree is the index modulation degree. The refractive index modulation degree of the photo-thermal refraction glass is 180-1250 ppm, preferably 500-1250 ppm.
The refractive index modulation degree increases with an increase in exposure dose, and thus the refractive index modulation degree can be adjusted according to the exposure dose. The higher refractive index modulation was obtained by increasing the crystallization temperature and the crystallization time, but the light absorption of the glass was also increased, and it was difficult to obtain the data shown in tables 1 to 4.
[ light absorption coefficient ]
Processing glass into 2-5 mm thick sheet with wavelength of 325nm and dosage of 2.5J/cm 2 After exposure to ultraviolet light, a heat treatment is performed. The crystallization temperature was 520℃and the crystallization time was 60 minutes. After the heat treatment is completed, the light absorption coefficient test is performed according to the standard GB/T7962.9-2010. The 780nm light absorption coefficient of the photothermal sensitive refractive glass of the invention is in the range of 0.030 cm to 0.050cm -1 Preferably 0.037-0.050cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The light absorption coefficient of 1064nm is in the range of 0.005-0.015cm -1 Preferably 0.009-0.015cm -1 。
Specific examples of glasses according to the invention are shown in tables 1 to 4 below.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
The above is an embodiment exemplified in this example, but this example is not limited to the above-described alternative embodiments, and a person skilled in the art may obtain various other embodiments by any combination of the above-described embodiments, and any person may obtain various other embodiments in the light of this example. The above detailed description should not be construed as limiting the scope of the present embodiments, which is defined in the claims and the description may be used to interpret the claims.
Claims (19)
1. A low melting temperature photothermographic, refractive glass, characterized in that: the cations of the photothermographic element glass comprise, in mole percent, the cations: si (Si) 4+ ：54.0～63.0％、Na + ：24～36％、K + ：0～2％、Zn 2+ ：0～6％、Al 3 + ：4～11％、B 3+ ：0～10％、Ag + ：0.005～0.10％、Ce 4+ ：0.005～0.10％、Sn 2+ ：0～0.1％、Sb 3+ ：0～0.1％；
The anions of the photothermographic element contain Br - 、O 2- And F - And anion-cation nuclear balance, wherein, in terms of mole percent of anions:
Br - /O 2- ×100：0.30～1.0、F - /O 2- ×100：3.0～5.8；
the mole percentage of the total of anions and cations is as follows: (Na) + +K + -F - -Br - )/2(Zn 2+ +0.5Al 3+ +0.5B 3+ )：1.695～1.815。
2. A low melting temperature photothermographic, refractive glass, characterized in that: the cations of the photothermographic element are, in terms of mole percent, represented by: si (Si) 4+ ：54.0～63.0％、Na + ：24～36％、K + ：0～2％、Zn 2+ ：0～6％、Al 3+ ：4～11％、B 3+ ：0～10％、Ag + ：0.005～0.10％、Ce 4+ ：0.005～0.10％、Sn 2+ ：0～0.1％、Sb 3+ :0 to 0.1 percent;
the anions of the photothermal sensitive refraction glass are formed by Br - 、O 2- And F - Composition, and anion-cation nuclear balance, wherein, in mole percent of anions:
Br - /O 2- ×100：0.30～1.0、F - /O 2- ×100：3.0～5.8；
the mole percentage of the total of anions and cations is as follows: (Na) + +K + -F - -Br - )/2(Zn 2+ +0.5Al 3+ +0.5B 3+ )：1.695～1.815。
3. A low melting temperature photothermographic element according to claim 1 or 2, characterized in that: in mole percent based on the sum of anions and cations (Na + +K + -F - -Br - )/2(Zn 2+ +0.5Al 3+ +0.5B 3+ )：1.700～1.815。
4. A low melting temperature photo-thermal glass as claimed in claim 1 or 2, characterized in that Si 4+ :54.0 to 60%, and/or Na + ：29～36％。
5. A low melting temperature photo-thermal glass as defined in claim 1 or 2, wherein Br is in mole percent of anions - /O 2- X 100:0.60 to 0.85, and/or F - /O 2- ×100：4.0～5.8。
6. A low melting temperature photo and thermal glass as defined in claim 1 or 2, wherein the melting temperature of the photo and thermal glass is 1255-1310 ℃.
7. A low melting temperature photo and thermal glass as defined in claim 1 or 2, wherein the melting temperature of the photo and thermal glass is 1255-1290 ℃.
8. The low-melting temperature photo-thermal folded glass according to claim 1 or 2, wherein the photo-thermal folded glass has a transition temperature Tg of 440-455 ℃.
9. The low-melting temperature photo-thermal refractive index glass according to claim 1 or 2, wherein the glass has a Tg of 440-450 ℃.
10. The low melting temperature photo-thermal refractive index modification glass according to claim 1 or 2, wherein the refractive index modulation degree of the photo-thermal refractive index modification glass is 180 to 1250ppm.
11. The low melting temperature photo-thermal refractive index modification glass according to claim 1 or 2, wherein the refractive index modulation degree of the photo-thermal refractive index modification glass is 500 to 1250ppm.
12. A low melting temperature photo and thermal refraction glass as set forth in claim 1 or 2, wherein the 780nm light absorption coefficient of the photo and thermal refraction glass is in the range of 0.030-0.050cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The light absorption coefficient of 1064nm is in the range of 0.005-0.015cm -1 。
13. A low melting temperature photo and thermal refraction glass as set forth in claim 1 or 2, wherein the 780nm light absorption coefficient of the photo and thermal refraction glass is in the range of 0.037-0.050cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The light absorption coefficient of 1064nm is in the range of 0.009-0.015cm -1 。
14. The method for producing a photothermographic, temperature-sensitive, refractive index glass having a low melting temperature according to any one of claims 1 to 13, wherein: after fully and uniformly mixing the raw materials, melting the raw materials into glass liquid at 1255-1310 ℃, clarifying and defoaming the glass liquid at 1450-1500 ℃, and then cooling the glass liquid to 1300-1350 ℃ for stirring and homogenizing; injecting the mixture into a mould preheated to 300-400 ℃ for molding, and introducing nitrogen to promote cooling of the surface of the glass, so as to ensure that the glass is not devitrified; and (3) cooling and shaping the glass, and putting the glass and the mold into an annealing furnace for cooling and annealing to obtain a colorless and transparent photo-thermal refraction glass block.
15. Use of a low melting temperature photothermographic element according to any one of claims 1 to 13, characterized in that: for the preparation of diffractive optical devices.
16. Use of a low melting temperature photothermographic element according to any one of claims 1 to 13, characterized in that: the method is used for preparing the volume Bragg grating device in the near infrared band.
17. A glass preform, characterized in that: a low melting temperature photothermographic element according to any one of claims 1 to 13.
18. An optical element, characterized in that: use of a low melting temperature photothermographic glass according to any one of claims 1 to 13 or use of a glass preform according to claim 17.
19. An optical instrument, characterized in that: use of a low melting temperature photothermographic element according to any one of claims 1 to 13 or of an optical element according to claim 18.
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|---|---|---|---|---|
| US4979975A (en) * | 1989-08-07 | 1990-12-25 | Corning Incorporated | Fast response photosensitive opal glasses |
| US6586141B1 (en) * | 2000-01-04 | 2003-07-01 | University Of Central Florida | Process for production of high efficiency volume diffractive elements in photo-thermo-refractive glass |
| US7326500B1 (en) * | 2000-01-04 | 2008-02-05 | University Of Central Florida Research Foundation, Inc. | Sensitization of photo-thermo-refractive glass to visible radiation by two-step illumination |
| CN101959816A (en) * | 2008-01-29 | 2011-01-26 | 康宁股份有限公司 | Polarizing photoreactive glass |
| CN108821569A (en) * | 2018-04-13 | 2018-11-16 | 苏州大学 | Laser holographic recording glass, diffraction optical device or hologram pattern product and preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7288495B2 (en) * | 2003-12-31 | 2007-10-30 | Corning Incorporated | Photorefractive glass and optical elements made therefrom |
| US20090190215A1 (en) * | 2008-01-29 | 2009-07-30 | Nicholas Francis Borrelli | Polarizing photorefractive glass |
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2022
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4979975A (en) * | 1989-08-07 | 1990-12-25 | Corning Incorporated | Fast response photosensitive opal glasses |
| US6586141B1 (en) * | 2000-01-04 | 2003-07-01 | University Of Central Florida | Process for production of high efficiency volume diffractive elements in photo-thermo-refractive glass |
| US7326500B1 (en) * | 2000-01-04 | 2008-02-05 | University Of Central Florida Research Foundation, Inc. | Sensitization of photo-thermo-refractive glass to visible radiation by two-step illumination |
| CN101959816A (en) * | 2008-01-29 | 2011-01-26 | 康宁股份有限公司 | Polarizing photoreactive glass |
| CN108821569A (en) * | 2018-04-13 | 2018-11-16 | 苏州大学 | Laser holographic recording glass, diffraction optical device or hologram pattern product and preparation method |
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